Reaction products of a meta-substituted phenol and formaldehyde



- 30 of recent resin acids on I Patented July 11, 1939 PATENT. OFFICE" REACTION PRODUCTS OF A META- SUBSTI- TUTED PHENOL AND FORMALDEHYDE Herbert Hone], Vienna, Austria,

assignor. to Helmuth Reichhold, Detroit, Mich, doing business, as Iteichhold Chemicals No Drawing. Application August 1, 1936, serial- '2 Claims.

My present invention relates to the production of homogeneous reaction masses from low molecular resols and high molecular substances as well as to resols of a definite type which are novel per se. I

An object of my invention consists in producing highly reactive, quickly hardenable resols which are yet capable of being chemically combined with the most various substances.

Another object of my invention consists in forming homogeneous reaction masses from 'particular resols and the most various substances. The latter may either be employed as modifying, more particularly plasticizin'g agents, heat .haidening products plasticized to any desired extent being thus obtainable; or they may be employed in such multiple proportions that permanently soluble reaction products are obtained which are distinguished by a substantially higher viscosity,

hardness and melting point respectively, and resistance to physical and chemical influences.

A further object of my invention consists in utilizing the reaction masses in a soluble stage as basicmateria'ls for molded articles or tum- 25 able masses, varnishes, binding media, etc., such as will beset forth more particularly hereinafter. It is known that low molecular resols, i. e., phenol-alcohols or -polyalcohols may formholnogeneous reaction masses heating. e Other high molecular carboxylic acids, such as the fatty acids of natural fatty glycerids, however, do not,.as a rule, form homogeneous reaction masses when heated with resols, but sago-' like to lumpy unmeltable resinous .masses separate out in themelt. In order .to efl'ect combi= nation of such fatty acids with resols 'it hasv been proposed to employ resols which are slowly hardenable per se (such as p-cresol dialcohol) or to substantially reduce the hardeningcapacity of the resol (phenolpolyalcohol) by certain chemical actions. When jointly heating such resols or modified resols withhigh molecular fatty acids esterification of alcoholic hydroxy groups and carboxyl groups take place. I

Furthermore it is 'knownthat homogeneous reaction masses also are formed on heating from neutral resins and otherneutral basic materials serving for the production of varnish and the like, such as fatty oils, waxes and various other ester-like bodies, on the one hand and resols on the other, provided the resols (crystalline, liquid, viscous or already resinous solid) derive from phenols which have but two particularly reactive positions in the molecule unoccupied: When with a multiple quantity In Austria August 1, 1935 working up drying oils or waxes, as a rule, a substituent having several saturated carbon atoms must be present inthe phenolic body, said substituent causing the mutual compatibility of The resinifying condensation reaction of 'phen01 (having. three particularly reactive positions) with formaldehyde (or its polymers) as is known, proceeds much faster than that of o- 'or p-cresol (having two particularly reactive positions) with is intended to mean the oand formaldehyde, otherwise analogous conditions provided.

Actually it is notpossible jointly to heat resols (phenol/poly/alcohols) deriving. from phenol with neutral substances or with fatty acids of natural oils or the like without the formation of absolutely inhomogeneous masses even if the quantity of formaldehyde has been reduced to the minimum quantity necessary for-the formation of hardenable products. v The reaction velocity of the phenol being considerably higher than that of the 0- or p-cresol, as is known, is surpassed to a multiple extent by that of the m-cresol, the reaction velocity of the symm. m-xylenol in turn being to a multiple extent ,higher than that of the m-cresol. The reaction velocity of the m-xylenol is so high that it is often difficult to,isolate a precautiously prepared phenolpolyalcohol. I E. g., traces of a strong mineral acid may lead to an immediate resinification intoan unmeltable mass.

Thus thegreat influence of methyl groups in m-position on the reactivity of the phenol' is obvious. Even the combination of a m-cresol polyalcohol with a recent natural resin acid causes difliculties; a combination with fatty acids derived from natural glycerids or even with neu-' tral substances is quite impossible.

It is therefore extremely surprising that, as I have now found, phenol alcohols deriving from the still more reactive symm. m-xylenol are capable of forming homogeneous reaction masses; not only with recent resin acids but also with acids derived from fatty oils, e. g., drying oils, or with similar high molecular carboxylic acids, such as naphthenic acids. Thus it appears that, due .to the presence of a second methyl group in mposition, on the one hand the resinification ve- -locity is considerably increased whereas on the other hand the capability of being chemically from phenol or cresol mixtures only allow the adcombined with other substances is nevertheless increased, homogeneous reaction masses being formed thereby. In contradistinction to the known process mentioned above no esterification (indicated by the decrease of the acid number) takes place in the course of the reaction between the aforesaid phenolalcohol and acids of fatty oils or the like.

Furthermore I have found by systematic experiments that resols deriving from phenols having' larger substituents in'm-positions, are capable of being chemically combined also with other substances mentioned hereinbefore such as neutral resins and fatty oils.- It is s'uflicient if only one of the m-positions carries a larger substltuent, the other may be unoccupied. Due to the introduction of larger groups, however, the resinification velocity decreases more and more as compared with that of the symm. m-xylenol or its phenolalcohols but first still surpasses, e. g., that of phenol.

This experience may be utilised very. advantageously in manifold ways. The possibility of adding plasticizing agents, as is known, plays an important role, e. g., in the production of plastic heat-hardening masses. While, however, resols dition of very small proportions of oily fatty acids, castor oil or physically similar substances, larger proportions being exuded during the hardening process, according to my present invention resols equal or even superior as to the hardening capacity may be modified by the incorporation of the hereinbefore mentioned substances in anyv proportion desired, even, e. g., with drying oils. Particularly when employing the last mentioned substances products are obtained which are also excellently adapted for being used as basic materials for heat hardening varnishes and the like. The hardening takes place at relatively low temperatures. The hardened films show an exceedingly high elasticity sistance against water and .chemical agents and possess a very good adhesiveness. A furthered vantage of the resolsemployed according to my invention "consists also in their generally good light fastness which, as is known, in the case of condensation products obtained from common phenol is very defective.

Permanently soluble reaction masses are obtained only when employing very large propor- -tions of resin acids, acids derived from fatty 7 glycerids, neutral resins,'oils, etc.

The technical properties of these substances are substantially improved by this process. These reaction masses may advantageously serve as basic materials for varnishes and the like. reaction mass obtained from a carboxylic acid and a resol by the esteriiication with an alcohol prior to its further utilization.

The term compatibility of a resol with other substances as mentioned above, which term I will use hereinafter for the sake of abbreviation, is intended. to indicate the capability of being I chemically combined with said substances, homoof phenols from geneous masses being formed thereby. The type which the resols according to my invention are obtained is represented by the formula Y r on aromatic, hydroaromatic or aromatic nature (such as colophony-glycerolv and an extraordinary re-' A permanently soluble should be. suitably neutralized, e. g.,-

' portions is in which R. means a substituent while R means either hydrogen or a substituent. About the following rule may be established: L (1) A total of two C-atoms ma and R suffices to bring about compatibility with recent resin other high molecular: carboxylic acids.

(2) A total of three to four C-atoms of aliphatic or alicy iic nature sumces to bring about compatibility with substantially neutral high molecular substances (is) of aliphatic nature being rich in oxygen, e. g., glycerides of oxy-acids, (p) of ester, coumarone resins, phthalic acid resins).

(3) In individual cases four of such 'C-atoms. also suflice to bringabout compatibility with neutral high molecular substances of distinct aliphatic nature. such as drying oils, waxes, pitches (e. g., residues of petroleum and of the distillation of fatty acids), rubber and similar substances; the presence of five or more of such C-atoms in any case causes the compatibility with the said group of substances.

.The greater this number of C-atoms, the more manifold is ingeneral the compatibility of the resol.

The'above mentioned rule principally applies to the maximal hardening capacity, viz., that the phenolic body is combined with the maximum quantity of formaldehyde. The preliminary condition, however, is that the molecular size (con- 1 densation stage) of the resol is rather low. An

increase of the molecular weight, as a rule. considerably impairs its compatibility, so to speak pushes it to a lower range of compatibility: Decrease of the proportion of, combined formalde hyde, however, as a rule, pushes it in a higher range. The rule also applies to ,a mixture of phenols of the above described type.

The substituents R and R are not limited to saturated hydrocarbon radicals. They may, e. 3., contain oleflnic double linkages or, e. g., hydroxy or other oxygen containing'groups: the hydrocarbon radlcals may also be combined with the acids or acids derived from fatty glycerids or mixed aliphatic- Y benzene nucleus only indirectly, e. g., by oxygen or are examples for the substituents.

ucts, and on the other hand enable the combiningof as large proportions of formaldehyde as possible.

I When using strong alkaline catalysts and low reaction temperatures 2% to 3 mols formaldehyde, as a rule, may be compounded by the phenols employed according to my invention. or course, I also may employ a considerably larger quantity of formaldehyde whereby the time necessary for combining the above mentioned maximum proshortened (law of massaction).

It is important that alkaline catalysts such as sodium-, potassiumor barium hydroxide be carefully eliminated from the resol prior to its chemical combination with other substances, since on the one hand they generally increase the resiniflcation velocity in an undesired way, and on the other hand lead to disturbing secondary reactions. Weak catalysts such as ammonium and 7 excellent, air drying, varnish being highly resisthexamethylenetetramine respectively mayremain in the condensation'product.

. solvents escape. The heating is continued until In particular cases I add strong acids in catalytical proportions to the combination product of the resol and the other substance before carrying to completion the condensation in order to'accelerate it.

I may further influence the properties of the resols in that in conjunction with the phenols used according to my present invention I also subject other phenols to the condensation with formaldehyde. The co-use of phenols having but two particularly reactive positions in the molecule unoccupied is of particular importance. Even small proportions of such phenols may often considerably improve the compatibility of the resols with a certain group of substances mentioned above. Instead of starting from such a mixture of phenols I may also combine the separately formed resols whereupon I interact this mixture with the other substance.

The following examples are intended to more clearly illustrate the process:

Example 1 10 parts of s'ymm. m-xyle'nol, 30 parts of formaldehyde (40% vol.) and 1 part of sodium hydroxide are combined under cooling. The clear solution is left for two to three days at, room temperature and is than shaken in the presence of benzene and alcohol with a quantity of hydrochloric. acid equivalent to the alkali and with some acetic acid. The watery layer which still contains formaldehyde employed in excess is separated from the benzene-alcoholic solution of the condensation product in a suitable way.

10 to 15 parts of a mixture of fatty acidsobtained from linseed 'oil or another drying oil are carefully heated to about 110-120" C. and. the solution of the condensation product is gradually introduced at constant temperature, whereby the a resinous mass is obtained which at ordinary temperature is free of tackiness. It is readily soluble in various solvents, e. g., in aromatic hydrocar'bons. With the application of heat and pressure the mass is converted into an extraordinarily elastic unmeltable product.

The not yet hardened mass is particularly adapted as a base for stove enamels, cements, adhesives and the like.' On heating the thin film coat besides the hardening i due to condensation also a hardening caused by 'oxydation processes may ha accelerated by the oxydation and polymerisation of the fatty acid used takes place .so that the films acquire an extreme hardness and yet a high elasticity. The

addition of a dryer.

Y Ezamplez.

The solution of the condensation product obtainedaccording to Example 1 is combined with raised up to about 200 100 parts of ricininic acid (acid number 195) at about 120 C. The temperature is then gradually C. whereby the condensation reaction is carried to completion. The reac- 'tion mass (111 parts) that no esterification ofthe ricininic acid has taken place. with 11 to 12 parts of glycerol at 200 250 esterification product which is soluble, white spiritconstitutes a viscous mass which after thinning and after the addition of dryers yields an drying varnishes,

' plies for various neutral resins.

is of thickly liquid appear- 1 ance and has an acid number of 175. This proves The reaction mass is then esterifled C. The e. g., in

(M. P. 76-77 C.) is condensed for room temperature with formaldehyde with theaid of a strong alkali whereupon the catalyst is carefully eliminated.

several days at a multiple quantity of The condensation product obtained is capable of a chemically being combined not only with resin acids or fatty acids and the like but also with various neutral resins such as colophony-glycerol ester as well as with castor oil in reaction masses being formed thereby.

In order to obtain, e. g., a hardenable plastic mass the condensation product is carefully heated to about 100-120 C. with half of its weight of castor oil until a desired consistency is attained. On heating for a prolonged period suitably at higher temperatures with the application of pressure a very elastic plastic mass is formed;

any proportion, clear In order to obtain a heat-hardenable varnish v and the like it is in a similar way combined, e. g., with 1 to 3 parts of-a viscous resin (mixed ester) obtained from the interaction of phthalic acid, linseed oil fatty acid and glycerol.

In orderto obtain a high melting, oil soluble copal substitute it is heated, e. g., with 5 to 10 times the quantity of colophony-glycerol ester to temperatures above 200 C.

Example 5 (3) hydroxy-propyl phenol,

riootrn 3) cmom .C2H5

(M. P. 103-110 c.) is stirred o'r shaken with twice the quantity of formaldehyde, 40% vol.,

' and a smaller quantity of barium hydroxide until all has gone into solution apart from a slight turbidity caused by barium carbonate, [After about two weeks the barium hydroxide is converted into the carbonate by passing through the charge acurrent of carbon dioxide, which is removed in a suitable way. The condensation product is so readilysoluble in water that it cannot be separated even by the addition of salt; The watery solution isconcentrated in vacuo to about twice the. weight of phenolic body em-.

ployed.

When introducing the concentrated watery so-' 'lution into heated castor oil entirely homogene- 'ous reaction masses are obtained. The same ap- The condensation product may be utilized and worked up-respectively in a similar way as the condensation product inExample 4.

1 mol condense ith about 250 grms. or more of formaldehyde (40% by vol.) as in Example 4.

The viscouscondensation product yields homogeneous reaction masses on melting together with resin esters, phthalic acid resins or castor oil, These areinsoluble and soluble respectively according to the proportions used. Thus harden- 130 rms.) of (3,5) diethyl-pheno1 is a stituted by a 'plasticizing agents .which' are very able masses 'of any desired plasticity or heat hardenable varnishes and the like may be obtained from the condensation product. Cir it is heated with larger quantities of cheap resins in order to increase their hardness and melting point.

By melting it together with 1000 grms. of resin ester (M. P. 68-75 C.) a very hard and highly viscous resin melting between 120-135 C. is obtained. This resin is readily oils. Oil varnishes prepared therefrom dry without showing yellowing phenomena.

Example 7 (3) -rnethyl-(5) -isopropyl phenol (M. P. 48- 49 C.) is-condensed as in the preceding example.

The thickly liquid condensation product may not only be combined by heating with substances mentioned in Example. 6, butalso with drying oils. There is at most formed a very slight turbidity. The condensation product therefore may be utilized in the most manifold ways. An excellent heat-hardenable varnish may be obtained, e. g., by carefully melting together the condensation product with 200-300 grms. of

China-wood oil at about 130 0., until an only slightly tacky mass is formed. It is soluble, e. g., in white spirit. The mass becomes extremely hard when heated in thin layers (varnish film) for about '1 hour at 150 only condensation but also oxidation and polymerization take place.

The condensation product is compatible inter alia also with natural or artificial rubber.. The condensation product freed from water is kneaded together with.,e. g., 2 kg. of creperubber on a calender or the like, vulcanizing agents, and filling materials being added if desired, until a smooth mass of homogeneous appearance is formed. By heating it in a way usually employed for working up rubber, a product is obtained which distinguishes by a much higher tensile strength and less swellin as compared with a product whichis obtained from the same starting materials without, how-- ever, employing the condensation product.

Almost the same results are obtained when the pure phenolic bodies mentioned above are subtechnical product which is contaminated by'small portions of homologues which have but two particularly reactive positions unoccupied. It is for example a consequence of this admixture that theresol obtained yields entirely clear reaction products with drying oils; this applies also to the employment of such large proportions of oil that a permanently soluble reaction product is formed also when carrying the reaction to completion. Such reaction products yield extremely resistant varnish films after suitable addition of dryers.

Example 8 If the phenoliobody employed in Example 6 is substituted by the isomeric m-butyl phenol or by S-butyloxyphenol, (30135341906610, 1. e., the'monobutyl ether oi the resorcinol) condense tion products are obtained the properties of similar to those of the condensation product obtained according to Example 6. The products may be brought into reaction, e. g., with castor-oil or certain resins, hompgeneous masses being formed thereby, but not with excess quantities of drying oils. A smaller proportions! 9 drying oil. e. g., 100 grmaoi linseed oil, may, however. be combined with the condensation product by carefully heating (about at soluble in drying C., since on heating not amnesia 100 C.) A clear, extremely hard fllm is obtained if a thin coat (varnish film) of. the combination 7 product is exposed to an increased temperature.

amp 9 (3) c-hydroxyamylphem (HO.C6H4,(3) CH(OH) .C4H9) is condensed with twice the quantity of aqueous formaldehyde (40% vol.) with the aid of a strong alkali for about one perature.

The reaction mixture is neutralized and a quantity of common salt sufllcient for saturation is added in order to isolate the condensation product. The reaction mixture is then heated on the water bath until turbidity occurs. This is caused by portions of the condensation product which have been converted into higher molecular stages. Benzene and some propyl alcohol are added and the reaction mixture is shaken. The said portions of the condensation product are taken up by the solvents whereby the watery layer is cleared again. The heating andshaking is continued until no further turbidity occurs in the watery layer. The solution of the condensation product is then separated from the watery layer.

The resol obtained in this way 'yields homoe genous reaction masses withdryin'g oils, pitches, rubber, etc., the condensation product may be utilized in most various ways, e. g., as in Exproduct may be utilized in an analogous way.

Example 1o to two weeks at room tem- .A resol obtained from (3)-isoamyloxyphenoi (boiling point lid-160 C. at 12 mms.)] shows a very similar behaviour.

The resol may be technically utilized, e. g., in the way described inExample 7 very similar results being obtained.

If the production of I nish basic material) with a drying oil, e. g., linseed oil, is aimed at which is soluble also after the condensation reaction is carried to completion at least eight times the quantity as compared with the weight of phenolic body is to be employed since otherwise-gelatinization of the reaction mixture occurs.

When 10. parts of a rosin lycerol ester are melted together with such a quantity of the condensation product as corresponds with 1 part of the phenol used, a resin is formed the softening point of which is 36 C. higher than that of the rosin ester used. These data' show that the resol is considerably superior to one which derives sitions' unoccupied.

Example 11 Very similar results a m the Examples '1, s 0'.

The resol is produced, e. g., in a way as described in Example 6.

maybe obtained if, e. g., the following phenolic are prepared with the aid of a strong alkaline bodies are used. catalyst, the latter being removed after condensation between the phenol and formaldehyde has Tart butyl s'hydmxyphenylcarbmol been performed The generallyemployedaqueous 5 (3) HO-C6H4.CH('OH)-C-(CH3) 3] formaldehyde, partly at least, may be replaced IL 34) hexylphenol (=amy1 3 hydroxy .by its anhydrous polymeric forms. The catalyst phenyl ketone HO.C6H4-(3)CO.C5H11) may replaced by smug garlic bases such as methylamine. Also when using weak Hexyl (3) hydroxyphenyl carbmol 3 hy alkalies, such as ammonia, good results may be droxyheptyl-p obtained, In the latter case the neutralization- 10 HO.CoH4.( 3)CH(OH).CsHia I of the catalyst may be omitted. The formaldecyclohexyk3 hydroxyphen,ylcarbmolr hycle'may be replaced not only by its polymers but also by another methylene containng agent, such (=Ho-CH4-(3)CH(OH) -C6H11I) as hexamethylenetetramine, similar results be- 3 heptenylphenol ing obtained thereby as from formaldehyde and 15 ammonia. (HO'C6H"(3)CH=CH'C5H11) Apart irom those substances which have been VI. Decyl-3-hydroxyphenyl-carbinol (3) -hymentioned in the preceding specification and exdroxy-undecylphenol] amples ior chemically being combined with the resols, many other more or less closely related (3)CH(OH)'CIH2I substances may be employed, whereby the char-' 20 y r Xyrnyloxybenzene acter of the final product may be still more va-p [(1)HO C6H4 (3)CmH17= ried. Apart from the nature of these substances the character of the final product depends to a 425 resommol mohobomyl etheflvery large extent also upon the relative propor- The condensation products (resols) are pretions of these Substances and the r8801, finally, pared, e. g., according to the methods described in w also UPOII the further Chemiwl P ythe Examples 5, 6 or 9. If higher temperatures sical treatment. of the combination product.

are avoided as far as possible suiiiciently' low Instead Of acids derived from fatty yfl s; molecular resols are obtained which are compatia there m 6- at be e p y s [so ble with all classes of substances mentioned in mt high molecular fatty c ds, acids de i ed the description. l from waxes, natural resin acids or mixtures Example 12 thereof with acids derived from fatty .oils, ar-

In contradisuhction to resols which derive from tiiicially obtained masses which contain many h l free carboxylic groups, such as a still acid reaca5 ,g gfig fiiittti'i 31ifiiiii lfiiltitftifii g tion product obtained from poiyvaient alcoholsl the resols which derive from. the phenols used polybasic and monobasic carboxylic acids or their cording to my present invention depends to a natural glycerides (an example for such a prod- M very large extent upon the molecular size (conf bemg densation stage) of the resols (compare the de- COOCLLCH OH 000 40 scription'above). This is illustrated, e. g., by the a J 2 r following experiment: 7 QOOH The phenols: (a) As used in Example 9, wherein R means a saturated or unsaturated 5 (b) IIIin Example 11; radical).

V1111 Example L The term high molecular substances carrying .-which are homologues in the narrowest sense, are carhoxyhc groups as used herein means the each condensed with a multiple proportion of hereihbefhre'mehhohed suhsthhces of high aqueous formaldehyde in the presence of sodium 'leclhar .w h which chhtalh groups 50 hydroxide or the like at 40 C. for about four to and then" obvlohs chhh'hcal eqmvalehtsfi days on neutralizing charges very Instead of castor oil, coiophony glycerol ester,

viscous or, solid resinous, water insoluble concoumamne resin. c ssg), there may, e. g., densauon products are obtauiem be employed blown fattyoils (e. g., blown linseed while when proceeding in a a r as oil) or partial glycerol esters of higher fatty acids,

scribed in Examples 9 or 5 very low molecular more Particularly h h h' 9 liquid resols are obtained all of which are capable of ahiehc esters or natural f h per se heurchemicany being combined (Compatible) with 'tr al (such as dammar, maiti resin), or neutral drying 011s and other neutrafsubstances belong; artificial resins obtained by condensation or polymg to the same u n,-t compatibility of merisation or both,-such as phenolic resins (no- 60 resols obtained according-to present example volaks) polymerized aromatic hydrocarbonsle. g., is substantially reduced. The resol obtained from h hr ym products of ester" (a) is neither compatible with drying oils nor llke nature -(such as vmyl or W 00111901111115);

with t oil but only with acidic substances also urea-formaldehyde resinsand other aminesuch as resinacids or acids derived from fatty aldehydwesins'are compatiblemore Particular" 65 f,

zlycerids; that obtained from (b) is compatible, 1y t vd qph resqls s as mentwned e, g., with castor oil and other substances of that above. In individual cases suEh resins as men- I class but incompatible with drying oils, etc; Only tioned hereinbefore suitably are combined with the condensation product obtained from the, the resol n ,a dissolved sta phenolic) which carries'a particularly large sub-- h term Substantially neutral hi mo ec- 70 stitu'ent is compatible also with drying oils and ular substances (on) Of aliphatic nature being rich other neutral substances of distinct aliphatic in xy n, (p) of aromatic, h r m mix d nature, e. g.,-rubber. aliphatic-aromatic nature as used herein, means In the preceding examples special reference has the hereinbefore mentioned substantially neutral been made to resols and their utilization, which j substances of high molecular weight of (a) ali- 1 5 obvious chemical equivalents.

' claimed rubber and other depolymerization products or rubber, gutta percha, overpolymerized oils, Iactice maybe combined with the resols in an appropriate way. I

The term neutral high,molecular substances of aliphatic nature as used herein means the hereinbefore mentioned substances of high molecular weight and aliphatic nature and their The combination products may be utilized in the most various ways. Products obtained by incomplete condensation, which by complete condensation become insoluble and infusible, i. e., which are heat hardening, may be hardened 'in molds with or without the addition of flllingmaterials, products adapted for the most various uses being obtained. A further use consists, e. g., in the manufacture or floor and wall coverings and the like. The solution 0! such a hardenable product may not only serve as heat hardening varnish or for enamels. cements (i. e.', ior common coatingsrlmown in the varnish field) but. also as adhesives or binding agents (e. g, for water resistant abrasives), impregnating agents for wood, paper textiles and other porous materials. Instead of the solution there may also be emalso serve as basic ployed the product itself liquifled by heat, for

the purposes mentioned.

But also permanently soluble end products obtained by complete condensation may serve for the said purposes at least when containing drying oils or the radicals thereof. Permanently soluble end products without drying properties may materials for varnishes and lacquers'(e. g., as plasticizingagents) if they are compatible with nitrocellulose, cellulose ethers, chlorinated rubber and similar film forming materials. with nitrocellulose generally is brought about by a relatively large number of esterlike groups.

What I claim is:

1. A resol obtained from a methylene containing agent and a phenol having all particularly reactive positions (0-, 0-,. pto the phenolic hydroxy group) unoccupied but at least one of the meta-positions occupied by a saturated substituent of aliphatic nature containing more than two carbon atoms capable of reaction with (1) high molecular substances carrying carboxylic groups, (2) substantially neutral high molecular substances (or) of aliphatic nature being rich in oxygen, (,9) of aromatic, hydroaromatic, mixed aliphatic-aromatic nature, and (3) neutral high molecular substances of aliphatic nature, to'produce homogeneous reaction products.

2. A resoi as set forth in claim 1, wherein the substituent contains at least 4-5 carbon atoms.

HERBERT HGNEL.

The compatibility of an end product 

